EP0322290A2 - Process for the allylation of perhaloalkyl, perhaloalkoxy, perhaloalkylthio anilines in the presence of metals - Google Patents
Process for the allylation of perhaloalkyl, perhaloalkoxy, perhaloalkylthio anilines in the presence of metals Download PDFInfo
- Publication number
- EP0322290A2 EP0322290A2 EP88403213A EP88403213A EP0322290A2 EP 0322290 A2 EP0322290 A2 EP 0322290A2 EP 88403213 A EP88403213 A EP 88403213A EP 88403213 A EP88403213 A EP 88403213A EP 0322290 A2 EP0322290 A2 EP 0322290A2
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- EP
- European Patent Office
- Prior art keywords
- process according
- palladium
- chosen
- allyl
- chloride
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 15
- 239000002184 metal Substances 0.000 title claims abstract description 15
- 150000001448 anilines Chemical class 0.000 title claims abstract description 8
- 238000005937 allylation reaction Methods 0.000 title abstract description 8
- 150000002739 metals Chemical class 0.000 title abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- -1 allyl halide Chemical class 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- VIUDTWATMPPKEL-UHFFFAOYSA-N 3-(trifluoromethyl)aniline Chemical compound NC1=CC=CC(C(F)(F)F)=C1 VIUDTWATMPPKEL-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- SLFVYFOEHHLHDW-UHFFFAOYSA-N n-(trifluoromethyl)aniline Chemical compound FC(F)(F)NC1=CC=CC=C1 SLFVYFOEHHLHDW-UHFFFAOYSA-N 0.000 claims description 3
- WTAPZWXVSZMMDG-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 WTAPZWXVSZMMDG-UHFFFAOYSA-N 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 claims 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N Vilsmeier-Haack reagent Natural products CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ATHHXGZTWNVVOU-UHFFFAOYSA-N monomethyl-formamide Natural products CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 101100074998 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) nmp-2 gene Proteins 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003880 polar aprotic solvent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- FALCMQXTWHPRIH-UHFFFAOYSA-N 2,3-dichloroprop-1-ene Chemical compound ClCC(Cl)=C FALCMQXTWHPRIH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(II) acetate Substances [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Substances Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- LQFLWKPCQITJIH-UHFFFAOYSA-N n-allyl-aniline Chemical compound C=CCNC1=CC=CC=C1 LQFLWKPCQITJIH-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
Definitions
- the present invention relates to a process for the preparation of N-allyl perhaloalkyl, perhaloalkoxy, perhaloalkylthio anilines. It relates more particularly to a process for allylation of metatrifluoromethylaniline in the presence of metals.
- allylation yield is around 50%. This yield is of paramount importance when the raw materials are very expensive. Thus, in the case of metatrifluoromethylaniline, it is sought to obtain yields as high as possible. In the case of aminophenols this criterion is much less important.
- metatrifluoromethylaniline is a compound which is highly deactivated from the chemical point of view, the substitution of which is much more difficult than that of derivatives such as paraphenylenediamine, which is activated and therefore promotes substitutions.
- the present invention has achieved this dual objective. Its subject is a process for allylating perhaloalkyl, perhaloalkoxy, perhaloalkylthioanilines, characterized in that an aniline is brought into contact in a solvent medium. perhaloalkylated, perhaloalkoxylated or perhalogenothioalkylated with an allyl halide in the presence of a catalytic amount of a metal chosen from palladium, copper and nickel.
- perhaloalkylated, perhaloalkoxylated or perhalogenothioalkylated aniline is understood to mean the compounds of general formula (I) below: in which : - A represents a covalent bond, an oxygen or sulfur atom, - X1, X2, X3, X4, X5 each represents an identical or different halogen atom, - n is equal to 0.1 or 2, - R represents a hydrogen atom, a halogen, an alkyl group having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, aryl.
- the process of the present invention is catalyzed as indicated above by a metal chosen from palladium, copper and nickel.
- metals can be in the form of metal salts in the oxidation state I or II, in particular chloride, sulfate, acetate, oxide.
- these salts, oxides and complexes there may be mentioned - palladium chloride, - cuprous chloride, - cupric chloride, - nickel chloride, - palladium sulfate, - copper sulphate - nickel sulfate, - cupric oxide, - palladium acetate, - cupric acetate, - Palladium chloride complexed with benzonitrile.
- the metal can also be in the oxidation state O in metallic form such as copper powder for example or in the form of a complex such as palladium dibenzylideneacetone. Among the metals mentioned, it is preferred to use palladium.
- the allyl halide is preferably chosen from allyl chloride and allyl bromide, it is still preferred to use allyl chloride.
- the present invention can be implemented in polar aprotic solvents such as: - N-methylpyrrolidone (NMP), - N, N-dimethylformamide (DMF), - N-methylformamide (NMF), - N, N-dimethylacetamide (DMA), in ethers such as: - tetrahydrofuran (THF), - petroleum ether, - methyltertiobutylether, in nitriles such as: - benzonitrile, - acetonitrile, in optionally halogenated aromatic solvents such as: - toluene, - xylene, - chlorobenzene, - dichlorobenzene, in aliphatic solvents preferably containing 5 to 10 optionally halogenated carbon atoms such as: - cyclohexane, - heptane, in alcohols and preferably in ethanol.
- NMP N-methylpyrrolidone
- polar aprotic solvents it is preferred to use polar aprotic solvents.
- a molar ratio of allyl halide to aniline of between 1 and 2 and a molar ratio of the metal catalyst to aniline of between 0.01 and 0 , 5 preferably between 0.05 and 0.2.
- the concentration of aniline in the solvent is preferably between 100 g and 500 g per liter.
- reaction conditions it is preferred to work between 50 and 120 ° C. for a period which can vary between 2 and 24 hours.
- the mixture is stirred and heated to 75 ° for variable times. After cooling, 5 ml of sodium hydroxide are added. The organic products are extracted with 5 ⁇ 5 ml of isopropyl ether. The organic phase is filtered through clarcel and diluted to 25 ml to be determined by internal calibration by gas phase chromatography.
- Example 1 Solvent influence Test Catalyst Solvent Time TT m-TFMA RT N-Allyl RT N, N-Diallyl Comparison 5 - 0 ⁇ -0-0 ⁇ 2:30 a.m. 0.3 Traces - 19 Cu 0 ⁇ -0-0 ⁇ 2:30 a.m. 18.4 77 16 Comparison 6 - DMF 2:30 a.m. 17.8 76.8 - 20 Cu DMF 2:30 a.m. 67.6 62.9 16.7 Comparison 7 - Toluene 2:30 a.m. 1.1 Traces - 21 Cu Toluene 2:30 a.m.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
La présente invention concerne un procédé de préparation de N-allyl perhalogénoalkyl, perhalogénoalcoxy, perhalogénoalkylthio anilines. Elle concerne plus particulièrement un procédé d'allylation de la métatrifluorométhylaniline en présence de métaux.The present invention relates to a process for the preparation of N-allyl perhaloalkyl, perhaloalkoxy, perhaloalkylthio anilines. It relates more particularly to a process for allylation of metatrifluoromethylaniline in the presence of metals.
Il est connu par exemple selon le brevet US 2 286 678 de condenser le bromure d'allyle sur un aminophénol en présence de carbonate de potassium dans un solvant alcoolique.It is known, for example, according to US Pat. No. 2,286,678 to condense allyl bromide on an aminophenol in the presence of potassium carbonate in an alcoholic solvent.
Le rendement d'allylation se situe aux environs de 50 %. Ce rendement présente une importance capitale lorsque les matières premières sont très couteuses. Ainsi dans le cas de la métatrifluorométhylaniline on cherche à obtenir des rendements aussi élévés que possible. Dans le cas des aminophénols ce critère est beaucoup moins important.The allylation yield is around 50%. This yield is of paramount importance when the raw materials are very expensive. Thus, in the case of metatrifluoromethylaniline, it is sought to obtain yields as high as possible. In the case of aminophenols this criterion is much less important.
Il est aussi connu d'après le brevet US 3 668 254 de préparer les N-haloallyl p. phénylène diamines par condensation sur l'amino-4 diphénylamine de dichloro-2,3 propène en présence de quantités stoechiométriques de triéthylamine et en l'absence de solvant.It is also known from US Pat. No. 3,668,254 to prepare N-haloallyl p. phenylene diamines by condensation on the amino 4-diphenylamine of 2,3-dichloro propene in the presence of stoichiometric amounts of triethylamine and in the absence of solvent.
Les rendements annoncés dans ledit brevet sont toujours très faibles, environ 38 % dans le seul exemple. La technique décrite dans ce brevet n'était donc pas transposable à des matières premières aussi onéreuses que la métatrifluorométhylaniline.The yields announced in said patent are still very low, around 38% in the single example. The technique described in this patent was therefore not transposable to raw materials as expensive as metatrifluoromethylaniline.
Il faut aussi noter que la métatrifluorométhylaniline est un composé fortement désactivé du point de vue chimique dont la substitution est beaucoup plus difficile que celle des dérivés tels que la paraphénylènediamine qui elle est activée et favorise donc les substitutions.It should also be noted that metatrifluoromethylaniline is a compound which is highly deactivated from the chemical point of view, the substitution of which is much more difficult than that of derivatives such as paraphenylenediamine, which is activated and therefore promotes substitutions.
L'industrie se trouve devant un double problème, obtenir une N-allylation de la métatrifluorométhylaniline avec des rendements corrects sur un produit qui est beaucoup plus difficile à substituer que ceux qui sont décrits dans l'art antérieur.The industry is faced with a double problem, obtaining an N-allylation of metatrifluoromethylaniline with correct yields on a product which is much more difficult to replace than those which are described in the prior art.
La présente invention a permis d'atteindre ce double objectif. Elle a pour objet un procédé d'allylation des perhalogénoalkyl, perhalogénoalcoxy, perhalogénoalkylthioanilines caractérisé en ce que on met en contact en milieu solvant une aniline perhalogénoalkylée, perhalogénoalcoxylée ou perhalogénothioalkylée avec un halogénure d'allyle en présence d'une quantité catalytique d'un métal choisi parmi le palladium, le cuivre et le nickel.The present invention has achieved this dual objective. Its subject is a process for allylating perhaloalkyl, perhaloalkoxy, perhaloalkylthioanilines, characterized in that an aniline is brought into contact in a solvent medium. perhaloalkylated, perhaloalkoxylated or perhalogenothioalkylated with an allyl halide in the presence of a catalytic amount of a metal chosen from palladium, copper and nickel.
On entend par aniline perhalogénoalkylée, perhalogénoalcoxylée ou perhalogénothioalkylée les composés de formule générale (I) suivante :
- A représente une liaison covalente, un atome d'oxygène ou de soufre,
- X₁, X₂, X₃, X₄, X₅ représente chacun un atome d'halogène identique ou différent,
- n est égal à 0,1 ou 2,
- R représente un atome d'hydrogène, un halogène, un groupe alkyle ayant 1 à 4 atomes de carbone, alcoxy ayant 1 à 4 atomes de carbone, aryle.The term perhaloalkylated, perhaloalkoxylated or perhalogenothioalkylated aniline is understood to mean the compounds of general formula (I) below:
- A represents a covalent bond, an oxygen or sulfur atom,
- X₁, X₂, X₃, X₄, X₅ each represents an identical or different halogen atom,
- n is equal to 0.1 or 2,
- R represents a hydrogen atom, a halogen, an alkyl group having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, aryl.
Ces anilines sont toutes des composés fortement désactivés dont la substitution est difficile.These anilines are all highly deactivated compounds whose substitution is difficult.
Il est encore connu d'après le brevet US 3 642 902 de réaliser l'allylation de l'aniline, composé non désactivé, par des complexes du chlorure de bis(allylpalladium). Les rendements d'allylation sont toujours faibles, ils sont de l'ordre de 25 %.It is also known from US Pat. No. 3,642,902 to carry out the allylation of the aniline, a compound which is not deactivated, with complexes of bis (allyl palladium) chloride. The allylation yields are always low, they are around 25%.
Il est aussi connu d'après les articles de ARESTA parus dans Synth. React. Inorg. Met. Org. Chem., 9(2), 157-174 de 1979 et dans le Journal of Chemical Society Dalton, (1977), 493 de préparer des complexes du palladium II avec les N-allylanilines. Ces complexes sont facilement détruits avec libération de méthylacétylène et d'un complexe Pd-aniline. A la lecture de ces trois derniers documents, il était impossible d'envisager un procédé industriel mettant en oeuvre des métaux tels que le palladium du fait des risques de formation de ces complexes qui conduisent à une rétrogradation irréversible des N-allylanilines formées à la moindre augmentation de température.It is also known from the articles of ARESTA published in Synth. React. Inorg. Met. Org. Chem., 9 (2), 157-174 of 1979 and in the Journal of Chemical Society Dalton, (1977), 493 to prepare complexes of palladium II with N-allylanilines. These complexes are easily destroyed with the release of methylacetylene and a Pd-aniline complex. On reading these last three documents, it was impossible to envisage an industrial process using metals such as palladium because of the risks of formation of these complexes which lead to an irreversible retrogradation of the N-allylanilines formed at the slightest increase in temperature.
Aussi il a été tout à fait surprenant de constater qu'en mettant en contact une aniline perhalogénoalkylée, perhalogénoalcoxylée ou perhalogénothioalkylée avec un métal choisi parmi le palladium, le nickel et le cuivre il n'y ait aucune dégradation de la N-allylaniline formée et un excellent rendement calculé sur l'aniline transformée.Also, it was quite surprising to find that by contacting a perhaloalkylated, perhaloalkoxylated or perhalogenothioalkylated aniline with a metal chosen from palladium, nickel and copper there is no degradation of the N-allylaniline formed and an excellent yield calculated on the processed aniline.
Le procédé de la présente invention est catalysé comme indiqué précédemment par un métal choisi parmi le palladium, le cuivre et le nickel. Ces métaux peuvent se présenter sous forme de sels métalliques à l'état d'oxydation I ou II notamment de chlorure, de sulfate, d'acétate, d'oxyde. Parmi ces sels, oxydes et complexes on peut citer
- le chlorure de palladium,
- le chlorure cuivreux,
- le chlorure cuivrique,
- le chlorure de nickel,
- le sulfate de palladium,
- le sulfate de cuivre
- le sulfate de nickel,
- l'oxyde cuivrique,
- l'acétate de palladium,
- l'acétate cuivrique,
- le chlorure de palladium complexé par le benzonitrile.The process of the present invention is catalyzed as indicated above by a metal chosen from palladium, copper and nickel. These metals can be in the form of metal salts in the oxidation state I or II, in particular chloride, sulfate, acetate, oxide. Among these salts, oxides and complexes there may be mentioned
- palladium chloride,
- cuprous chloride,
- cupric chloride,
- nickel chloride,
- palladium sulfate,
- copper sulphate
- nickel sulfate,
- cupric oxide,
- palladium acetate,
- cupric acetate,
- Palladium chloride complexed with benzonitrile.
Le métal peut aussi se présenter à l'état d'oxydation O sous forme métallique telle que la poudre de cuivre par exemple ou sous forme de complexe tel que le palladium dibenzylidèneacétone. On préfère parmi les métaux cités utiliser le palladium.The metal can also be in the oxidation state O in metallic form such as copper powder for example or in the form of a complex such as palladium dibenzylideneacetone. Among the metals mentioned, it is preferred to use palladium.
L'halogénure d'allyle est choisi de préférence parmi le chlorure d'allyle et le bromure d'allyle, on préfère encore utiliser le chlorure d'allyle.The allyl halide is preferably chosen from allyl chloride and allyl bromide, it is still preferred to use allyl chloride.
La présente invention peut être mise en oeuvre dans les solvants aprotiques polaires tels que :
- la N-méthylpyrrolidone (NMP),
- le N,N-diméthylformamide (DMF),
- le N-méthylformamide (NMF),
- le N,N-diméthylacétamide (DMA),
dans des éthers tels que :
- le tetrahydrofurane (THF),
- l'éther de pétrole,
- le méthyltertiobutyléther,
dans des nitriles tels que :
- le benzonitrile,
- l'acétonitrile,
dans des solvants aromatiques éventuellement halogénés tels que :
- le toluène,
- le xylène,
- le chlorobenzène,
- le dichlorobenzène,
dans des solvants aliphatiques contenant de préférence 5 à 10 atomes de carbone éventuellement halogénés tels que :
- le cyclohexane,
- l'heptane,
dans des alcools et de préférence dans l'éthanol.The present invention can be implemented in polar aprotic solvents such as:
- N-methylpyrrolidone (NMP),
- N, N-dimethylformamide (DMF),
- N-methylformamide (NMF),
- N, N-dimethylacetamide (DMA),
in ethers such as:
- tetrahydrofuran (THF),
- petroleum ether,
- methyltertiobutylether,
in nitriles such as:
- benzonitrile,
- acetonitrile,
in optionally halogenated aromatic solvents such as:
- toluene,
- xylene,
- chlorobenzene,
- dichlorobenzene,
in aliphatic solvents preferably containing 5 to 10 optionally halogenated carbon atoms such as:
- cyclohexane,
- heptane,
in alcohols and preferably in ethanol.
Parmi ces solvants on préfère utiliser les solvants aprotiques polaires.Among these solvents, it is preferred to use polar aprotic solvents.
En ce qui concerne les quantités de réactifs mises en oeuvre on préfère utiliser un rapport molaire d'halogénure d'allyle à l'aniline compris entre 1 et 2 et un rapport molaire du catalyseur métallique à l'aniline comprise entre 0,01 et 0,5 de préférence compris entre 0,05 et 0,2.As regards the amounts of reagents used, it is preferred to use a molar ratio of allyl halide to aniline of between 1 and 2 and a molar ratio of the metal catalyst to aniline of between 0.01 and 0 , 5 preferably between 0.05 and 0.2.
La concentration de l'aniline dans le solvant est comprise de préférence entre 100 g et 500 g par litre.The concentration of aniline in the solvent is preferably between 100 g and 500 g per liter.
En ce qui concerne les conditions réactionnelles on préfère travailler entre 50 et 120°C pendant une période pouvant évoluer entre 2 et 24 heures.As regards the reaction conditions, it is preferred to work between 50 and 120 ° C. for a period which can vary between 2 and 24 hours.
La présente invention sera plus complètement décrite à l'aide des exemples suivants qui ne doivent en aucun cas être considérés comme limitatifs.The present invention will be more fully described with the aid of the following examples which are in no way to be considered as limiting.
Dans les exemples suivants on entend par :
TT = le taux de transformation du produit initial
TT = the transformation rate of the initial product
Dans un réacteur de 30 ml, on introduit
- 0.65 g de m. trifluorométhylaniline (4 m Moles),
- 0,61 g de chlorure d'alkyle (8 m Moles),
- 2 ml de solvant,
- 0,4 mM de catalyseur.The following are introduced into a 30 ml reactor
- 0.65 g of m. trifluoromethylaniline (4 m Moles),
- 0.61 g of alkyl chloride (8 m Moles),
- 2 ml of solvent,
- 0.4 mM of catalyst.
Le mélange est agité et chauffé à 75° pendant des temps variables. Après refroidissement, on ajoute 5 ml de soude N. Les produits organiques sont extraits par 5 x 5 ml d'éther isopropylique. La phase organique est filtrée sur clarcel et diluée à 25 ml pour être dosée par étalonnage interne en chromatographie phase gazeuse.
Dans réacteur de 30 ml, on introduit
- 0,65 g de m. trifluorométhylaniline (4m Moles),
- 0,3 g de chlorure d'allyle (4 m Moles),
- 2 ml de solvant,
- 0,4 mM de catalyseur.Into a 30 ml reactor, the following are introduced
- 0.65 g of m. trifluoromethylaniline (4m Moles),
- 0.3 g of allyl chloride (4 moles),
- 2 ml of solvent,
- 0.4 mM of catalyst.
Le mélange est chauffé et agité 2 H 30 à 75°. Après refroidissement, on ajoute 5 ml de soude N. Les produits organiques sont extraits par 5 x 5 ml d'éther isopropylique. La phase organique est filtrée sur clarcel et diluée à 25 ml pour être dosée par étalonnage interne.
Dans ces exemples a été étudié l'influence de différents solvants dans les conditions de l'exemple 1.
Claims (10)
- A représente une liaison covalente, un atome d'oxygène ou de soufre,
- X₁,X₂,X₃,X₄,X₅ représente chacun un atome d'halogène identique ou différent.
- n est égal à 0,1 ou 2,
- R représente un atome d'hydrogène, un halogène, un groupe alkyle ayant 1 à 4 atomes de carbone, alcoxy ayant 1 à 4 atomes de carbone, aryle.2 - Process according to claim 1 characterized in that the aniline corresponds to the following general formula (I):
- A represents a covalent bond, an oxygen or sulfur atom,
- X₁, X₂, X₃, X₄, X₅ each represents an identical or different halogen atom.
- n is equal to 0.1 or 2,
- R represents a hydrogen atom, a halogen, an alkyl group having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, aryl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT88403213T ATE89259T1 (en) | 1987-12-23 | 1988-12-16 | PROCESS FOR THE ALLYLATION OF PERHALOALKYL, PERHALOALKOXY, PERHALOALKYLTHIOANILINES IN THE PRESENCE OF METALS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8718011A FR2625196B1 (en) | 1987-12-23 | 1987-12-23 | PROCESS FOR ALLYLATION OF PERHALOGENOALKYL, PERHALOGENOALCOXY, PERHALOGENOALKYLTHIO ANILINES IN THE PRESENCE OF METALS |
| FR8718011 | 1987-12-23 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0322290A2 true EP0322290A2 (en) | 1989-06-28 |
| EP0322290A3 EP0322290A3 (en) | 1990-05-02 |
| EP0322290B1 EP0322290B1 (en) | 1993-05-12 |
Family
ID=9358213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88403213A Expired - Lifetime EP0322290B1 (en) | 1987-12-23 | 1988-12-16 | Process for the allylation of perhaloalkyl, perhaloalkoxy, perhaloalkylthio anilines in the presence of metals |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4956496A (en) |
| EP (1) | EP0322290B1 (en) |
| JP (1) | JPH02739A (en) |
| AT (1) | ATE89259T1 (en) |
| DE (1) | DE3880997T2 (en) |
| FR (1) | FR2625196B1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5189220A (en) * | 1988-07-29 | 1993-02-23 | Rhone-Poulenc Chimie | Process for preparing N-alkylanilines and N-allylanilines catalyzed by iodides |
| US5210305A (en) * | 1988-07-29 | 1993-05-11 | Rhone-Poulenc Chimie | Process for preparing n-alkylanilines and n-allylanilines |
| US5276443A (en) * | 1991-03-27 | 1994-01-04 | Xircom, Inc. | Parallel port multiplexor for PC parallel port |
| CN102040526A (en) * | 2010-11-26 | 2011-05-04 | 西北师范大学 | Preparation method of N,N-diallyl aniline |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3642902A (en) * | 1968-12-24 | 1972-02-15 | Monsanto Co | Allylamines from pi-allylpalladium complexes |
| US3914311A (en) * | 1973-06-15 | 1975-10-21 | Du Pont | Preparation of aromatic secondary and tertiary amines using a nickel complex catalyst |
| US4096185A (en) * | 1976-01-08 | 1978-06-20 | E. I. Du Pont De Nemours And Company | Preparation of p-aminobenzotrifluoride |
| EP0205391A1 (en) * | 1985-05-22 | 1986-12-17 | Rhone-Poulenc Chimie | Process for the preparation of N-alkenyl-M-trifluoromethyl anilines |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2286678A (en) * | 1942-06-16 | N-axkenxl-aminophenol | ||
| US3668254A (en) * | 1970-03-20 | 1972-06-06 | Monsanto Co | N-HALOALLYL-p-PHENYLENEDIAMINES |
| FR2689503B1 (en) * | 1992-04-03 | 1994-06-10 | Solvay | PROCESS FOR PURIFYING A HYDROFLUOROALKANE. |
-
1987
- 1987-12-23 FR FR8718011A patent/FR2625196B1/en not_active Expired - Lifetime
-
1988
- 1988-11-15 JP JP63286912A patent/JPH02739A/en active Pending
- 1988-12-16 DE DE8888403213T patent/DE3880997T2/en not_active Expired - Fee Related
- 1988-12-16 EP EP88403213A patent/EP0322290B1/en not_active Expired - Lifetime
- 1988-12-16 AT AT88403213T patent/ATE89259T1/en not_active IP Right Cessation
- 1988-12-23 US US07/288,880 patent/US4956496A/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3642902A (en) * | 1968-12-24 | 1972-02-15 | Monsanto Co | Allylamines from pi-allylpalladium complexes |
| US3914311A (en) * | 1973-06-15 | 1975-10-21 | Du Pont | Preparation of aromatic secondary and tertiary amines using a nickel complex catalyst |
| US4096185A (en) * | 1976-01-08 | 1978-06-20 | E. I. Du Pont De Nemours And Company | Preparation of p-aminobenzotrifluoride |
| EP0205391A1 (en) * | 1985-05-22 | 1986-12-17 | Rhone-Poulenc Chimie | Process for the preparation of N-alkenyl-M-trifluoromethyl anilines |
Non-Patent Citations (3)
| Title |
|---|
| (HOUBEN-WEYL) "METHODEN DER ORGANISCHEN CHEMIE", "vierte, völlig neu gestaltete Auflage", vol. XI/I, Stickstoffverbindungen II, 1957, Georg Thieme Verlag, Stuttgart, DE * |
| (HOUBEN-WEYL) "METHODEN DER ORGANISCHEN CHEMIE", 4. Auflage, vol. XI/I, Stickstoffverbindungen II, 1957, Georg Thieme Verlag, Stuttgart, DE * |
| CHEMICAL ABSTRACTS, vol. 83, no. 1, 7 juillet 1975, page 755, no. 9062t, Columbus, Ohio, US; N.M. MORLYAN et al.: "Copper(I) chloride, a catalyst for substitution of a halogen by amines in allylic halides", & ARM. KHIM. ZH. 1975, 28(1), 75-6 * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3880997T2 (en) | 1993-09-16 |
| DE3880997D1 (en) | 1993-06-17 |
| JPH02739A (en) | 1990-01-05 |
| US4956496A (en) | 1990-09-11 |
| FR2625196A1 (en) | 1989-06-30 |
| ATE89259T1 (en) | 1993-05-15 |
| EP0322290A3 (en) | 1990-05-02 |
| FR2625196B1 (en) | 1990-04-27 |
| EP0322290B1 (en) | 1993-05-12 |
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